1. Field of the Invention
The present invention relates to a novel green pigment composition. Specifically, the present invention relates to a novel green pigment composition that is environmentally safe because any hazardous substance will not be generated upon wasting and/or recycled use, and at the same time has a clear shade and an excellent stability.
2. Description of the Related Art
In recent years, since the environmental pollution has become serious due to the chemical substances, the promotion for solving the problem has been proposed from the viewpoint of the raw materials. Even the coloring materials such as a pigment or the like are not exception for it, the product liability for the safety of the decomposed type and secondary products which generate at the time of wasting and thermal disposal processing for the human body and environments has been examined. There has been a movement in which halide directly causing the generation of PCB and dioxin at the time of burning has to be removed from the raw materials of the products daily used.
The coloring materials of green used as a representative ecological color, at present, in almost all of the cases, are obtained by using chromium oxide green made of an inorganic pigment or cobalt chromium green, chlorination of an organic pigment or, brominated copper phthalocyanine pigment. However, since the former contains chromium, there is a problem upon wasting, the use is limited and in recent years, organic pigments have substituted for it. The latter also contains chlorine and bromine at a high ratio in the chemical structural formula, therefore, for example at the time of burning it, it has a drawback that generates a large quantity of harmful gas. However, at present, especially an organic pigment at an economical cost and having a clarity and an excellent durability which can substitute for phthalocyanine green has not been found yet, therefore, these are at present widely used as the main products for use in green colorants.
However, in recent years, in some fields, a movement intended to use only the materials, which are not the source of causing the generation of hazardous substances, has emerged. For example, as disclosed in Japanese Patent Application Charged-Open No. 2000-7974, there has been also an attempt for manufacturing a green coloring material by dispersing a blue pigment such as phthalocyanine blue or the like and a yellow pigment not containing a halogen atom into the vehicle, separately or at the same time.
However, the manufactured products of green colorants only by mixing a plurality of pigments, these are neither sufficient for endurance nor sufficient for hue being not clarified, only a green coloring material in which the separation of the colors is readily occurred particularly when it is manufactured into an ink or paint has been obtained.
The present inventors have accomplished the present invention as a result of deliberate studies of systems of green pigment compositions in hopes of solving such problems as mentioned above concerning green colorants. Specifically, having continued to make attempts to let pigment derivative materials cover particles of green pigments obtained by co-wet milling or co-dry milling of halogen-free blue pigments and halogen-free yellow pigments in the presence of milling medium, the present inventors have finally and surprisingly reached a pigment composition that is clear as a colorant and has no color separating tendency, which had not been achieved at all before the invention.
A primary object of the present invention is to provide a green pigment having no practical problems even if considering the safety and sanitary problems and environmental pollution problems while maintaining the clarified shade, an excellent light resistance and excellent heat resistance. Another object of the present invention is to provide a method of manufacturing such a green color pigment composition.
The present invention is a novel green pigment composition comprising (a) a green pigment comprising a mixture of fine particles of a halogen-free blue pigment and fine particles of a halogen-free yellow pigment and (b) a halogen-free pigment derivative.
The green pigment may be a product obtained from a co-fining process of the halogen-free blue pigment and the halogen-free yellow pigment. The pigment derivative contained in the green pigment composition is preferably in an amount of 0.2-30 wt. % based on an amount of the green pigment. The green pigment may be a product obtained by co-wetgrinding the halogen-free blue pigment and the halogen-free yellow pigment. The green pigment may also be a product obtained by co-drymilling the halogen-free blue pigment and the halogen-free yellow pigment.
The blue pigment may be at least one selected from the group consisting of phthalocyanine pigments, threne pigments, and indigo pigments. The yellow pigment may be at least one selected from the group consisting of azo, benzimidazolone, isoindoline, flavanthrone, anthrapyrimidine, anthraquinone, quinolinoquinolone, fluoroflavin and fluoruvin pigments. The pigment derivative preferably has a colorant residue and/or a triazine group.
The present invention is also a pigment dispersion comprising the green pigment composition as above-mentioned and a vehicle component.
In the green pigment composition according to the present invention, the particles of the blue pigment, the particles of the yellow pigment and the pigment derivative may be in a state of homogeneous mixture in their particle size order. Also in the green pigment composition according to the present invention, average particle sizes of primary particles constituting the blue pigment and the yellow pigment are preferably both 0.1 micron or less.
In general, pigment dispersion is a fine particle dispersion system in which each fine-size primary particle is in itself an assembly of crystallites of pigment molecules and in turn each pigment aggregate dispersed is one made of a plurality of such primary particles. In order to realize, by color mixing, a high quality green pigment composition not resulting in color separation or sedimentation, it is considered that it is essential to uniformly disperse, at their particle level of fineness, different kinds of pigment particles and secure the stability. The present inventors have considered that it may be difficult, when considering the circumstance confronted, a system composed of fine particles and where strong interfacial effect is present therefore, to attain such a desired state in the system, solely by means of the simple mixing processes of particles conventionally conducted.
A pigment immediately after being synthesized is typically composed of large particles having a size of 10 micron or more. Such a large particle is made to be fined in the subsequent pigmentation process. The fining process can be recognized as a process in which specific surface area of each pigment particle increases and the number of unstable surface molecules also increases, accordingly. Due to the existence of an extremely large number of such surface molecules, the pigment particles fined are temporarily put under an unusual condition that is thermodynamically extremely unstable and has high energy. Therefore when pigment particles of the same type, which have the same molecular structure and crystal structure and have thus an extremely high affinity each other, are once placed in a state of being finely divided and mixed, the particles tend to readily and rapidly agglomerate each other to realize an energetically stable state. In a pigment system where it has been realized based on a color mixing effect, such affinities between particles of the same kind will compete with those between particles of different kinds, and will work, as a result, to deprive of them the opportunity for mutually coming close to (or further intimately contacting) and homogeneously mixing with each other. The present inventors have considered that the consequence was just the green pigments that have been conventionally obtained and of low qualities where, for example, color separation and sedimentation easily proceed and also in a passage of time degradation proceeds rapidly further.
In the present invention, in order to appropriately cut off the agglomeration between particles of the same type, give the opportunity of closer approximations between pigment particles of different types and give them the stability in a mixed state, a specific substance, which is what we call xe2x80x9cpigment derivativexe2x80x9d, is used. xe2x80x9cPigment derivativexe2x80x9d used herein is considered a substance, a chemical compound, which has an affinity to at least one of the blue pigment and the yellow pigment used, has a color development characteristic which is not problematic with the normal color development of the pigment used (or substantially being colorless), and still further, does not have a halogen atom in the molecular structure. xe2x80x9cPigment derivativexe2x80x9d is considered as such an element as described above if it will be understood from its functions. It is further desirable that it has an excellent affinity for vehicle component used upon preparing an ink. As one example of such a xe2x80x9cpigment derivativexe2x80x9d, a substitution product substituted by substituents having an excellent affinity for an ink vehicle component typically used of the pigment skeleton of at lease one of the blue pigment or yellow pigment used, for example, sulfonic acid group, sulfoamide group, aminomethyl group, phthalimidemethyl group is considered.
As already described, the same kind of pigment particles already fined has a tendency of reciprocally and swiftly agglomerating each other when particularly inclusion such as a binder resin or the like does not exist. Therefore, it is appropriate that an introduction of xe2x80x9cpigment derivativexe2x80x9d used in the present invention to the system of the relevant pigment is performed prior to the point in time when the opportunity of such agglomerates of the same kinds of particles are proceeded or at least on the way of its proceeding. In other words, after the agglomerate of the same kinds of particles is sufficiently proceeded, even if a xe2x80x9cpigment derivativexe2x80x9d is further added at least as it is and mixed, it will be, in general, difficult to obtain a pigment composition of the present invention. In order to hinder the agglomerate occurred between the similar kinds of pigment particles, it is effective to perform the fining process en bloc in a mixture state without performing the fining of each pigment (pigmentation) separately and then mixing both.
A green pigment composition of the present invention can be realized via appropriate preparation processes. Once the xe2x80x9cpigment derivativexe2x80x9d is incorporated into a pigment dispersion system as intended, the stability of the energy state of the system is realized, at this time, the direct agglomerate of the same type of pigment particles is hindered, the stable color mixture state will be realized and maintained.
As indicated below, the present inventors have obtained the identical positive results, however it is limited, at any case, on the basis of a variety of concrete material selection; that is a proof of validity as the technological concept of the present invention.
A green pigment composition of the present invention may be manufactured by complexing it in the step of fining the blue pigment and the yellow pigment, and then passing through the process of adding a pigment derivative to the obtained green pigment. In the pigment composition manufactured via these processes, its pigment particle is in a state of being covered with the relevant pigment derivative. Due to such a microscopic surfactant environment, a pigment composition according to the present invention indicates a significantly enhanced clearness, color strength and the stability of the dispersion comparing to the conventional green pigment composition without adding the pigment derivative. Particularly, in the case where a pigment derivative having the same pigment skeleton with the pigment used, the effect to be aimed at by a composition of the present invention is significantly obtained.
A green pigment composition of the present invention is different from the green colorants color-matched by simple color mixture at the time of conventional manufacturing of an ink and manufacturing of coating material. Specifically, a green pigment composition of the present invention is good at stability in storage, whose hue is clarified, whose high light resistance and high heat resistance are maintained, and since at the same time, a halogen atom is not contained in the composition at all, it is a safe, sanitary pigment composition having a good quality, not containing the environmental problems and not generating a hazardous chemical substance at the time of burning.
As a result of eagerly studying, the present inventors have found being capable of providing a color material maintaining the similar coloring as the coloring material using a poly-halogenated (chlorinated or brominated) phthalocyanine and still stable colorants by using in combination a blue pigment not containing a halogen atom and a yellow pigment not containing a halogen atom obtained by co-wet milling, and achieved the present invention. As a blue pigment used in the present invention, there is not any particular limitation if it is a blue organic pigment not containing a halogen atom, it can be used by defining the quality level by the color shade to be aimed at and by referring to the durability and economy required. Following are some of examples of blue pigments that may be used in the present invention, being indicated by their color index numbers (C.I. No.): C.I. PIGEMENT BLUE 15, C.I. PIGMENT BLUE 15:2, C.I. PIGMENT BLUE 15:3, C.I. PIGMENT BLUE 15:4, C.I. PIGMENT BLUE 15:5, C.I. PIGMENT BLUE 15:6, C.I. PIGMENT BLUE 16, C.I. PIGMENT BLUE 60, C.I. PIGMENT BLUE 64, and C.I. PIGMENT BLUE 66.
As for phthalocyanine pigments, those having Cu as a central metal element are typically used as blue pigments, although others that have Ni, Co, Fe, Si, Al or the like as a central metal element, or of metal-free type, also may be used. Depending on the color shade to be aimed at, various crystal types such as xcex1-type, xcex2-type, xcex5-type or the like may be used. However, copper phthalocyanine is preferable if one stands on an economical viewpoint.
Regarding yellow pigments, as long as it is a yellow organic pigment not containing a halogen atom, basically any of them may be used. However, in order to give an excellent light resistance and excellent heat resistance, the pigment not containing a halogen atom in the structure of benzimidazolone pigments, isoindoline pigments, flavanthrone pigments, anthraquinone pigments, quinolinoquinolone pigments, fluoroflavin pigments and fluoruvin pigments is preferable. The combination selected from the above-described pigment group may be used. Hereinafter, examples of yellow pigments, which may be used in the present invention, are indicated by the color index (C. I. No.) and general name. However, the present invention is not limited to these.
These are C. I. Pigment Yellow 1, 4, 5, 9, 24, 42, 65, 61, 62, 74, 100, 101, 104, 117, 120, 123, 129, 133, 139, 147, 148, 151, 155, 168, 169, 175, 180, 181, 182, 185, 192, 194 and 213, or quinolinoquinolone, dimethyl quinolinoquinolone, fluoflavin, dimethylfluoflavin and fluoruvin.
The pigment immediately after the synthesis is referred to as a crude pigment in almost all of the cases, which is a form not suitable for colorants and having a size. A crude pigment is typically fined and selected in a particle size in the additional treatment step called as pigmentation, processed into the most suitable size as a color material, and used for an ink and paint. For example, the size of the primary particle of copper phthalocyanine pigment used as a color material is less than 0.1 micron, whereas a crude copper phthalocyanine pigment obtained by the synthesis is a gigantic particle on the order of 10 to 200 microns. The size of it has to be controlled to a size practical as a color material on the order of 0.02 to 0.1 micron by performing a treatment called as pigmentation. In a method of manufacturing a green pigment composition indicated herein, a low cost, crude pigment which has not been pigmented is used as a starting material, via processing steps such as wet-milling, dry-milling or the like, then a green pigment is obtained. Since it is a procedure for realizing a color mixture pigment system starting from a crude pigment, for example, as described in Japanese Patent Application Charged-Open No.2000-7974, the relevant procedure is far more advantageous in its economy when comparing to the procedures of manufacturing a color mixture pigment system starting from a pigment commercially available, and a dispersion having more excellent suitability is obtained.
The blending ration of a blue pigment and a yellow pigment when a green pigment is manufactured can be adjusted depending upon the green shade to be aimed at. The range of the blue pigment: yellow pigment =90:10 to 10:90 is preferable and then desirably, in the range of 70:30 to 20:80.
In a method of preparing a green pigment of the present invention, a mixture in which a blue pigment powder and a yellow pigment powder has been previously mixed may be used. When charging into a wet milling equipment or a dry-milling equipment, the blue pigment and yellow pigment may be charged individually so that they are in the designated ratio.
As a method of wet-milling, concretely, a small amount of aqueous solvent is added as a lubricant to the mixture of the blue pigment, yellow pigment and an aqueous inorganic salt at the above-described blending ratio, strongly and mechanically kneaded and ground by grinder such as a kneader or the like into a fined pigment, and then the aqueous inorganic salt and aqueous solvent may be removed. The weight ratio of the aqueous inorganic salt to the pigment is in the range of 2 to 20:1, and more preferably in the range of 3 to 10:1. The weight ratio of the aqueous solvent to the pigment is in the range of 0.5 to 3:1, and more preferably in the range of 0.7 to 2. For the removal of the aqueous inorganic salt and aqueous solvent, after the kneaded mixture is put into water, agitated and made it into a slurry shape, filtrations and washings are repeated.
Examples of aqueous inorganic salts include sodium chloride, potassium chloride and sodium sulfate. Examples of aqueous solvents include 2-methoxy ethanol, 2-butoxyethanol, 2-(isopentyloxy) ethanol, 2-(hexyloxy) ethanol, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol, triethylene glycol monomethyl ether, liquid polyethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether and liquid polypropylene glycol.
The desirable temperature when wet-milling is, although it also depends upon the kinds of pigments used and blending ratio, typically in the range of 40 to 130xc2x0 C., and more preferably in the range of 60 to 120xc2x0 C. The wet-milling time depends upon the kinds of pigments, blending ratio and the green shade to be aimed at, however, usually may be in the range of 1 to 12 hours. The additional ratio of solvent, grinding material or the like and the grinding temperature are preferably adjusted so that the hue to be aimed at is obtained in the range of these. After completing the pigment mass grinded and ink milled is re-slurried in a large amount of water, depending upon the cases, heating is performed, after uniformed slurry is made, the grinding material and grinding solvent may be completely removed by performing filtrations and washings, and depending upon the cases, washing by the solvent such as methanol or the like. A wet cake of the green pigment composition to be aimed at may be obtained by passing through these processes.
In the case where a pigment is prepared by dry-milling, the known dry-milling equipment such as an attritor, a ball mill, a vibrating mill or the like may be used. The green pigment composition having the color shade to be aimed at may be obtained by performing the processing such as pigmentation and emulsion treatment to the green pigment grinded and obtained and selecting the particle size if it is necessary.
The term xe2x80x9cpigment derivativexe2x80x9d in the present invention means a compound consisted of an organic dye, a pigment or its precursor not containing a halogen atom. The term xe2x80x9cdyexe2x80x9d is referred to a pigment soluble in water or oil, and the term xe2x80x9cpigmentxe2x80x9d is referred to a pigment substantially insoluble in water and oil.
The pigment derivative may have a structure represented by the following general formula. The structure may be selected while considering the effect on a vehicle component used and the color balance to the green pigment. 
Q represents an organic pigment residue that does not contain a halogen atom. X1 and X2 are different from each other, and a hydrogen atom or a substituent indicated as follows; i and j independently represent an integer of 1 to 4, respectively. 
R1, R2 represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, respectively and independently. Or, R1 and R2 together may constitute a 5 or 6 member ring structure which may further contain N, O or S atom. R3, R4, R5 and R6 are a hydrogen atom, or an alkyl group having 1 to 30 carbon atoms. However, all of R3, R4, R5, and R6 are not to be hydrogen atoms. Y represents a hydrogen atom, xe2x80x94NO2, xe2x80x94NH2 or xe2x80x94SO3H. M represents a hydrogen atom or divalent or trivalent metal atom, m represents an integer of 0 to 4, L represents valence number of M, and n represents an integer of 1 to 8.
A represents direct bonding, xe2x80x94Oxe2x80x94, xe2x80x94Sxe2x80x94, xe2x80x94COxe2x80x94, xe2x80x94SO2xe2x80x94, xe2x80x94CH2NHCOCH2xe2x80x94, xe2x80x94CR7R8xe2x80x94, xe2x80x94SO2NR7xe2x80x94, xe2x80x94CH2NHCOxe2x80x94, xe2x80x94CH2NCONR7xe2x80x94 (R7 is an hydrogen atom, an alkyl group having 1 to 30 carbon atoms or an aryl group, R8 represents an alkyl group having 1 to 30 carbon atoms or an aryl group), or a divalent linkage group indicated by the following formula: 
Z1 represents direct bonding, xe2x80x94CONHxe2x80x94R9xe2x80x94, xe2x80x94SO2NHxe2x80x94R9xe2x80x94, or xe2x80x94CH2NHCOCH2xe2x80x94R9xe2x80x94 wherein R9 represents an alkylene group having 1 to 8 carbon atoms or an arylene group. Z2 represents xe2x80x94NHxe2x80x94 or xe2x80x94Oxe2x80x94. Z3 represents a hydroxide group, an alkoxy group or a substituent indicated by the following general formula: 
In the formula, each of R1, R2, Z2, n and Ym is as already described above. In the case where i represents 1, Z3 may represent xe2x80x94NHxe2x80x94Z1xe2x80x94Q.
X3 represents an amino group, X4 represents a hydrogen atom, an amino group, a nitro group, a hydroxide group, an alkoxy group, a carboxyl group, a sulfonic group, an alkyl group which may be substituted or not be substituted, or an alkenyl group which may be substituted or not be substituted. k represents an integer of 1 to 3, 1 represents an integer of 0 to 2.
Aryl group herein means a phenyl group or a naphthalene group, which may be substituted by an alkyl group or not be substituted. Arylene group herein means phenylene group or naphthalene group, which may be substituted by an alkyl group or not be substituted.
Preferable examples of an organic pigment residue Q include halogen-free colorant residues of phthalocyanine-type, threne-type, indigo-type, benzimidazolone-type, isoindoline-type, flavanthrone-type, anthrapyrimidine-type, anthraquinone-type, quinolinoquinolone-type, fluoroflavin-type, fluoruvin-type, diketopyrrolopyrrole-type, quinacridone-type, perylene-type, perinone-type and types of metal complex. Furthermore, pale yellow aromatic ring compounds such as those of naphthalene-type or anthraquinone-type, which generally may not be called a colorant, are also included.
These pigment derivatives may be synthesized by known methods such as those described in, for instance, Japanese Patent Application Published No. S39-28884, Japanese Patent Application Charged-Open No.S58-28303, Japanese Patent Application Charged-Open No.1-217078, Japanese Patent Application Published No.3-14073, or Japanese Patent Application Charged-Open No.11-199796 and the like. The pigment derivative preferably has a hue not changing or having less influence on the shade the green pigment used has originally produced. The pigment derivative is preferably a compound having the same colorant skeleton as that of the green pigment itself used. It is preferably colorless or pale yellow.
For a method of adding a pigment derivative, although the pigment derivative in a dried powder form may be added during the dispersion process of the green pigment, the pigment derivative may be used by previously mixing with the green pigment, preferably, it is added at the time when the pigment is sufficiently fined during wet-grinding or dry-milling, so that the particles of the green pigment are co-present and covered with the derivative material. Nonetheless, the method is not strictly limited to a certain one.
The preferable amount of addition of the pigment derivative is in the range of 0.2 to 30 wt. % with respect to the green pigment, and determined by the particle diameter, structure of the green pigment, the structure of the pigment derivative and further the vehicle composition used. It is preferable that the amount of addition is lesser, so long as the effect is suitably obtained, and it is more preferable that the amount is optimized in the range of 1 to 15 wt. %.
It is presumed that the added pigment derivative exerts to adsorb on the surfaces of fine particles of the green pigment present, prevent the separation between blue pigment particles and yellow pigment particles which constitute the green pigment, provide resin-adsorbing layers to pigment particles at the time when it is in a dispersion medium, and enhance the dispersion stability. Therefore, it is important to select a pigment derivative having a color skeleton. In order to promote the resin absorption, the affinity between the terminal structure of the pigment derivative and the vehicle for forming the dispersion is also important. From these viewpoints, it is desirable that the most suitable pigment derivative is selected.
In the step of wet-milling or dry-milling, other additives may be added in the range not inhibiting the object of the present invention. The resins may be used in combination in order to prevent a strong agglomeration which will occur at the time of drying the fined green pigment, and easily enable to disperse it into transparent resin or the like. The resins may be used in combination during the pigmentation of the present invention, thereby probably resulting in obtaining a softer fine particle comparing to this. As a resin used, it is preferable solid at room temperature and insoluble in water. Examples of resins include a natural resin, a modified natural resin, a synthesized resin, and a synthesized resin modified by a natural resin. For a natural resin, rosin is typically used. Examples of modified natural resins include a rosin derivative, a fibrous cellulose derivative, a rubber derivative, a protein derivative and oligomers thereof. Examples of synthesized resins include epoxy resin, acryl resin, maleic resin, butyral resin, polyester resin, melamine resin, phenol resin, polyurethane resin, and polyamide resin. Examples of the synthesized resins modified by a natural resin include a rosin-modified maleic resin and a rosin-modified phenolic resin. The usage amount of the resin is preferably in the range of 5 to 100 wt % with respect to the green pigment.
Furthermore, in the processing step, additives such as a pigment dispersing agent, a plasticizer or inorganic pigments such as calcium carbonate, barium sulfate, silica or the like except for the resins may be used in combination.
A vehicle component used for a pigment dispersion may be a vehicle for an offset ink, a vehicle for a gravure ink, a vehicle for a paint, a vehicle for a printed circuit board ink, a vehicle for a resist ink for a color filter, a vehicle for an ink jet, a resin for a toner, or a resin for a molded plastic.
A vehicle for an offset ink may be a vehicle in which a resin such as a rosin-modified phenolic resin, a rosin-modified maleic resin, a petroleum resin, an alkyd resin or the like is combined with soybean oil, tung oil, linseed oil as main components.
A vehicle for a photogravure ink may be a vehicle in which a resin such as a lime rosin resin, a polyamide resin, a vinyl chloride resin, a cyclized rubber, a urethane resin, an acryl resin, a maleic resin, a nitrocellulose is combined with a solvent such as an aliphalic hydrocarbon, an aromatic hydrocarbon, a halogenation hydrocarbon, an alcohol, a ketone, an ester, an ether, an ether-alcohol, an ether-ester and water as main components.
A vehicle for a paint may be a vehicle in which a resin such as a nitrocellulose lacquer, an aminoakyd resin, an acryl lacquer an aminoacryl resin, a urethane resin, polyvinylacetal resin, an epoxy resin, a polyester resin, a vinyl chloride resin, a vinylidene fluoride resin, a polyether sulfone resin is combined with a solvent such as an aliphalic hydrocarbon, an aromatic hydrocarbon, a halogenation hydrocarbon, an alcohol, a ketone, an ester, an ether, an ether-alcohol, an ether-ester and water as main components.
An ink vehicle for a printed circuit board may be a vehicle in which an unsaturated group containing a resin such as a polycarboxylic resin, a bisphenol A type epoxy compound, an ultraviolet ray hardening resin or thermal hardening resin is combined with a polymerization initiation agent and a solvent such as a ketone, an ester, an ether, an aliphatic hydrocarbon and an aromatic hydrocarbon as main components.
An ink vehicle for a resist ink for a color filter will be described as follows: Examples of thermal hardening resins and thermal plastic resins include a butyral resin, styrene-maleate copolymer, a vinyl polyacetate, a polyurethane based resin, a phenol resin, a polyester resin, an acryl based resin, an epoxy resin, celluloses and a urea resin. Photosensitive resins may contain a photocrosslinking group such as (metha) acryl compound, cinnamic acid is introduced via an isocyanate group, an aldehyde group, an epoxy group or the like into a linear polymer having a reactive substituent such as a hydroxyl group, a carboxyl group, an amino group and the like. A monomer, an oligomer or the like for forming a similar coating film with a resin by being hardened with radiation irradiation may be used. The ink vehicle may contain a photo-initiator, sensitizer, and solvent. Examples of such solvents include an aliphatic hydrocarbon, an aromatic hydrocarbon, a halogenation hydrocarbon, an alcohol, a ketone, an ester, an ether, an ether-alcohol, or an ether-ester solvents such as cyclohexanone, cellosolve acetate, diethylene glycol dimethylether, ethylbenzene, ethylene glycol diethyl ether, xylene, methylethyl ketone, and ethyl acetate.
An ink for printing, a coloring resist or the like is finally produced by performing the removal of large particles and/or contained dust which may be more than 5 xcexcm in size, preferably more than 1 xcexcm, more preferably more than 0.5 xcexcm, by means of a centrifuge, a sintering filter, membrane filter or the like.
As a vehicle for ink jet printing inks, a resin soluble in water such as an acryl resin, a styrene-acryl resin, a polyester resin, a polyamide resin, a polyurethane resin and a fluororesin, or an emulsion having dispersibility or colloidal dispersion resin may be used. A neutralizing agent such as ammonia, amine, inorganic alkali or the like is added to these resins according to the necessity. Examples of solvents used include water, ethylene glycol, polyethylene glycol, ethylene glycol monomethyl ether and substituted pyrrolidone. Alcohols such as methanol, ethanol, isopropyl alcohol and the like may be used for the purpose of accelerating the dryness after printing. Furthermore, an anion activating agent, a non-ion activating agent, a cation activating agent or an amphoteric ion activation agent may be used for enhancing the dispersing stability of an antiseptic agent, a penetrant, a chelate agent and a pigment.
Examples of resins for toners include polystyrene, a styrene-acryl copolymer, a chloride resin, a styrene-vinyl acetate copolymer, a rosin-modified maleic resin, a phenolic resin, an epoxy resin, a polyester resin, a low molecular polyethylene, a low molecular polypropylene, an ionomer resin, a polyurethane resin, a silicone resin, rosin ester and rosin.
Examples of resins for a molding plastic include polyolefin based resin such as polypropylene, polyethylene, an ethylene-propylene copolymer, a copolymer of xcex1-olefin and acrylic acid or maleic acid, an ethylene-vinyl acetate copolymer, a copolymer of ethylene and acrylic acid or maleic anhyride, a vinyl resin such as polyvinyl chloride and polyvinyl acetate, acetal resin such as formyl resin and butyral resin, acryl resin such as polyacrylonitrile and a methacryl resin, a styrol resin such as polystylene and acrylonitrile-butadiene-stylene copolymer, a polyester resin such as polyethylene terephthalate and polycarbonate, a nylon such as 6-nylon, an unsaturated polyester resin, an epoxy resin, a urea resin, a melamine resin, and a cellulose resin.
Furthermore, as a resin for the above-described variety of vehicles, a biogradable raw material such as starch-modified resin, cellulose/chitosan, polyhydroxy butyric acid, polycaprolactone, polylactic acid may be used.